High molecular weight bimodal polyethylene elastomers using N,N'-nickel catalysts appended with methoxy and trifluoromethoxy functionality

Abstract

Polyolefinic materials displaying bimodal molecular weight distributions are of interest since they can potentially provide mechanical toughness from the high molecular weight component without losing processability on account of the low molecular weight component. With this in mind, a series of nickel(II) complexes, [1-[2,6-{(4-MeOC6H4)2CH}2–4-(F3CO)C6H2N]-2-(ArN)C2C10H6]NiBr2 (Ar = 2,4-Me2C6H3Ni1, 2,6-Et2C6H3Ni2, 2,6-iPr2C6H3Ni3, 2,4,6-Me3C6H2, Ni4, 2,6-Et2-4-MeC6H2Ni5, 2,6-Me2C6H3Ni6) have been synthesized and have shown, following treatment with MMAO or Et2AlCl, excellent activity for the polymerization of ethylene (up to 19.87 × 106 g (PE) mol−1 for Ni4/Et2AlCl) generating high molecular weight branched polyethylene. More importantly, the elastomeric material produced using Et2AlCl as activator displays bimodal characteristics as well as low crystallinity and a medium to high branching density. By contrast, the material prepared using MMAO was more unimodal and showed higher crystallinity and lower branching density. Stress–strain and stress–strain recovery tests performed on the bimodal PE’s revealed a range of tensile properties with a sample prepared using Ni5/Et2AlCl combining both high tensile strength and high fracture strength (σ = 20.3 MPa, ε = 892.0 %). Conversely, a PE sample prepared using Ni4/Et2AlCl showed the highest elastic recovery with a stress relaxation (SR) value of 67.6 %. Besides branching analysis, molecular weight determinations and mechanical tests on the polymers, all nickel complexes and precursor 1,2-bis(arylimino)acenaphthenes, have been characterized by a combination of spectroscopic techniques, elemental analysis and in the cases of Ni1(OH2) and Ni4 by single crystal X-ray diffraction. A theory is also proposed to explain the observed bimodality.